DE2813659A1 - HIGH-QUALITY, ORGANOMETALLIC POLYMERS - Google Patents

Description

Applicant: International Business Machines

Corporation, Armon, N.Y. 10504

kd 'sue highly conductive organometallic polymer e

The invention relates to highly conductive organometallic polymers / in particular poly (metal) tetrathiofulvalentetrathiolates, Poly (metal) dithiomethoxy tetrathiofulvalenes and poly (metal) ethylene tetrathiolate. The compositions can be used as antistatic agents and as conductive coatings used in electronic assemblies.

The compositions of the present invention can be used as polymer derivatives of tetrathiopentalen and Tetraselenopentalens to be described. These compounds have the general formulas

1 2
in which XS or Se, Y and Y are 0, S or Se;

Z ¹ and Z ^{2 are} -SR, -SeR or - NC ^? 1 and the radicals R and R ^{1 are} H, alkyl or aryl, or both together form a ring; and An is the anion of a strong acid. Until recently, these connections were unknown. The compounds mentioned and their synthesis are described in German patent application P 27 59 137.3. It has also hitherto been assumed that polymerisation of these compounds is not possible. In particular, the production of metal-containing polymers from these compounds is not yet known.

The object of the invention is to provide poly (metal) tetrathiofulvalene tetrathiolate, poly (metal) dithiomethoxy tetrathiofulvalen, Poly (metal) ethyl tetrathiolate and the corresponding selenium compounds.

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The compounds according to the invention are in the claims 1 to 4 deposited.

The synthesis for preparing the compositions of the present invention is briefly given below.

2,5-diketo-i, 3,4,6-tetrathiopental (diketo-TTP),

the production of which is described in German patent application P 27 59 137.3, is as indicated there dimerized by treatment with trimethyl phosphite in benzene. The dimer (dimeric diketo-TTP)

C r - '' S. / S ^

is treated with either sodium ethylate or methyllithium to obtain the corresponding tetrathiofulvalene tetrathiolate;

That it is actually the tetrathiofulvalene (TTF) tetrathioanion is proven by further conversion to the known tetrathiomethoxy (TTF) derivatives, which after another independent method:

The tetrathiofulvalen-tetrathio-anion is then combined with a Metal salt converted to obtain a poly (metal) tetrathiofulvalene tetrathiolate:

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On the other hand, 2,5-diketo-1,3,4,6-tetrathiopental can be used treated with sodium ethylate or methyllithite under Obtaining the ethylene tetrathiolate salt:

By reacting the ethylene tetrathiolate salt with a The metal salt becomes poly (metal) ethylene tetrathiolate

obtain. The thiolate salts of 2,5-diketo-1,3,4,6-tetrathiopentalene and its dimer are bifunctional tetrahedral ligands and can be used with a large number of transition metals or other reactants are implemented to obtain polymeric systems in which the tetrathiolate ligand to the metal used as a reactant in an alternating sequence, as shown above, forms bridges.

Di-, tri-, and tetravalent metal salts react easily with either of the two tetrathiolate salts by adding them to Ethanol or other solvents reflux for several hours to give black powder which through simple filtration can be isolated. When a divalent metal ion is incorporated into the polymer by coordination, are two sodium ions for each repeating metal bis-dithiolene unit required to ensure overall charge neutrality, or it can other ions are used. Variations in the type of polymer are also possible, depending on the configuration of the Ligands arranged around the metal ion. In general ι are square, planar or tetrahedral arrangements

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, the common ones for bis-dithiolene metal systems; and similar configurations are expected for the polymer systems, particularly for metals such as Ni ²⁺ , Pd ²⁺ , Pt ²⁺ , Cu ^2+, and Zn ²⁺ . Inter-ligand configurations or twisted configurations ] are also possible. With a planar arrangement of the ligands around the metal ion, a planar polymer chain is expected, which leads to the advantageous interactions in the solid state. Other variations in the ligand arrangement are also possible, depending on the character of the metal ion. For example, higher coordination states than the tetravalent can be obtained, for example with metals such as Re, Mn, Cr and W, as well as bonding schemes in which the metal ion is divided between the polymer chains or is bound to other added coordination ligands. Metal-metal interactions between chains are also possible. Mixed oxidation states can occur in some of these coordination polymers, a factor known to result in high conductivity.

Various polyvalent metals can be copolymerized with any of the tetrathiolate salts to give mixed metal-polymer materials. It is also possible to polymerize a transition metal in different oxidation states at the same time. The organometallic polymer materials described are of considerable interest because they have interesting and unusual optical, magnetic, and electrical properties. In particular, the nickel: tetrathiofulvalene tetrathiolate polymer has a conductivity, measured on a pressed sample, of ^ 30 (ohm-cm) "", which is an unusually high value for an amorphous, organometallic polymer. When M in the polymer = Zn, Co, Fe or Pt, the resulting polymer is less conductive. There may be a wide range of possibilities conductivity ¹ gene metal be obtained depending on the used mehrwerti- ■. In Table I are conductivities,

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measured on the pressed sample at room temperature, some of the higher conductivity corresponding organometallic polymer materials described in the literature. It can be seen that the nickel tetrathiofulvalene tetrathiolate polymer has a conductivity that is several orders of magnitude greater. It is also noteworthy that the conductivities the neutral TTF and the nickel-bis-dithiolene compound, which are the constituents of the poly-nickel tetrathiofulvalentetrathiolate represent, each are much lower. Spectroscopic measurements of this polymer in KBr show strong electronic absorptions at 2900 a "and 3100 R, which are for the Dithiolene are characteristic and intense broad absorption in infrared, which is responsible for an electronic mechanism leading to the high conductivity of the Polymers contributes, is characteristic.

TABLE I.

Conductivities at room temperature , measured on pressed samples

link t ^σ ΗΤ _.
(Ohm-cm) 1Ο ¹ 3 χ χ 1θ " ⁶ > 7.5 10 " ¹² Poly- (nickel-tetrathiofulval-
tetrathiolate) (VI), M = Ni 1 χ Nickel-bis-dithiols Tetrathiofulvalene <; S-

COO

2M

+ 2

CO 0_
I = Cu ⁴² Ni ⁺² Co ⁺²

Cu + ²

CNH-Il '0

7.4 1O ~ ⁵ - 4.6 χ 1O ~ ⁸

3.2 χ 10

-1

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The starting materials 2,5-diketo-1,3,4,6-tetrathiopental and its dimer Δ ² ' ² -bis- (5-keto-1,3,4,6-tetrathiopental) (DiTTP) are prepared according to the following reaction sequence manufactured:

, CH:

2K ⁺ SC-O-CH

0 I! + Cl ₂ CH-C-OCH ₃ -

^X CH-OC -

CH ₃ CH,

CH ^

- S.

CH:

CH-C - OCH ₃

I) HoSO ₄ CONC. ί Z ^

2) H ₂ 0

Ο = ·

P (OMe),

benzene

.n 0

As can be seen, the synthesis of the starting materials involves the condensation of an alkyl dithiocarbonate salt with Methyl dichloroacetate. The condensation product is then cyclized through acid and water treatments. The method is described in detail in the above-mentioned German patent application P 27 59 137.3.

The tetrathiolate salts, which are used as intermediates in the present invention are prepared according to the following schemes:

0 =

or

O O =

> -O

0d.4CH ₃ Li

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These tetrathiolate salts can be reacted with a metal salt. The metal can be one or more of the polyvalent Metals Cu, Ni, Fe, Pt, Pd, Zn, Re, Mn, Cr, W and Co can be selected.

Many extensions of the synthetic methods given above are possible. For example, dimeric diketo-TTP can be treated with two equivalents of sodium ethylate or methyllithium to give the monoketo-dithioanion salt, which in turn can be treated with methyl iodide to give 2-keto-5- (4 ¹ , 5'-dithiomethoxy-1 ·, 3'-dithioliden-2'-yl) -TP. This material can then be treated with two equivalents of sodium ethylate or methyllithium to give the dithiomethoxy-TTP-dithioanion.

2NoOäth _n > - 0 -

or ^x s ^^ ~ s

2CH ₃ Li

CH ₃ X

IT

NS,

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The latter can be implemented with a large number of polyvalent metals, the new bis (tetrathiofulval) dithiolene metal complexes can be obtained according to the following formula:

In the formula, M is a polyvalent metal.

Example I.

Dimeric diketo-tetrathiopental has four equivalents reacted a solution of sodium ethylate in ethanol under nitrogen and refluxed for two hours. A dark solution of sodium tetrathiofulvalen (TTF) tetrathioanion is received. One equivalent of nickel acetylacetonate is added to this solution and the solution is poured over Boiled under reflux overnight. Black poly (nickel tetrathiofulvalene tetrathiolate) precipitates from the reaction mixture and is collected by filtration. It will be thorough washed with water, ethanol and acetone and dried under vacuum in an oven. The elemental analysis showed 15.1% Nickel in the composition. Spectral analytical measurements in KBr showed strong electronic absorptions at 2900 and 3100 8, which are characteristic of the dithiolene unit and have an intense broad absorption in the infrared spectral region. The conductivity, measured on a pressed sample, was 50 (ohm-cm) ".

Example II

The same procedure as in Example I is repeated with the exception that one equivalent of CuCl _{2 is} added, whereby a black precipitate of poly (copper-tetra-

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- ίο -

thiofulvalene tetrathiolate) is obtained. Elemental analysis for copper: 10.8%. Conductivity: 1.1 χ 1Ο ~ ¹ (ohm-cm) " ^1. Broad electronic absorption (KBr) is observed at 10,000 A *.

Example III

The same procedure as in Example I is followed except that one equivalent of FeCl., Is added, whereby a black precipitate of poly (iron tetrathiofulvalene tetrathiolate) is obtained. Elemental analysis for iron: 17.0%. Conductivity: 5.6 χ 10 ~ ⁵ (ohm-cm) " ^1. A broad electronic absorption (KBr) is observed at 11,000".

Example IV

The same procedure as in Example I is followed except that one equivalent of CrCl _{3 is} added to give a black precipitate of poly (chromium tetrathiofulvalene tetrathiolate). Elemental analysis for chromium: 6.4%. Broad electronic absorption (KBr) is observed at 10,000 S.

Example V

The same procedure as in Example I is followed except that one equivalent of CuCl ₂ and two equivalents of nickel acetylacetonate are added to give a black precipitate of poly (nickel-copper tetrathiofulvalene tetrathiolate). Elemental analysis for: nickel 2.4%, copper 16.6%. Conductivity, measured on a pressed sample: 40 (0hm-cm)

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- 11 Example VI

The same procedure as in Example I is followed with the exception that two equivalents of zinc chloride (ZnCl_) are added, whereby a brown-black precipitate of poly (zinc tetrathiofulvalene tetrathiolate) is obtained. Elemental analysis for zinc: 28.1%. Broad electronic absorption (KBr) is observed at 10,500 A *.

Example VII

The same procedure is followed as in Example I with the exception that two equivalents of K ₃ PtCl _{4 are} added, whereby a brown-black precipitate of poly (platinum tetrathiofulvalene tetrathiolate) is obtained. Elemental analysis for platinum: 24.2%. Conductivity, measured

-4 -1 on a pressed sample: 10 (ohm-cm). Broad electronic absorption is observed at 11,000 S.

Example VIII

The same procedure is followed as in Example I except that one equivalent of FeCl ₂ and one equivalent of FeCl- are added to give a black precipitate of poly (iron tetrathiofulvalene tetrathiolate). Elemental analysis for iron: 10.9%. Conductivity, measured on a pressed sample: 1.3 χ 10 (0hm-cm)

Example IX

By treating 2,5-diketo-tetrathiopentalen with four Equivalents of a solution of sodium ethylate in ethanol under nitrogen and boiling under reflux for two hours, a dark solution of sodium-ethylene ! tetrathioanions received. This solution becomes two

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Equivalents of nickel acetylacetonate are added and the solution refluxed overnight. The black poly (nickel-ethylene-tetrathiolate) precipitates out of the reaction mixture and is collected by filtration and intensively with it Washed with water, ethanol and acetone. Elemental analysis for nickel: 11.0%. Conductivity, measured on a pressed

-3 -1
Sample: 10 (ohm-cm). Electronic absorptions (KBr) are observed at 3900 and 12,500 8.

> - 0

H ₃ CS-

2-keto-5- (4 ' _f 5'-dithiomethoxy-1', 3 ^I -dithioliden-2'-yl) -1,3,4,6-tetrathiopental or -2-keto-5- (4 ·, 5'-dithiomethoxy-1 ', 3'-dithiolidene-2'-yI) -TTP. By treating part of the dimeric diketo-TTP in 250 parts of anhydrous tetrahydrofuran with 2 equivalents of methyllithium (1.45 M in ether) at ice temperature for a period of two hours and then adding three parts of methyl iodide, a solution is obtained from which by chromatography 2-keto-5- (4 ", 5 -dithiomethoxy-1 ', 3'-dithioliden-2-yl) -TTP can be isolated on silica gel. F (in C °) 178 ° Z; Molecular weight, calculated 385,818; found (mass spectrometry) 385.819.

Example XI

By treating 2-keto-5- (4 *, 5'-dithiomethoxy-1 ', 3'-dithioliden-2-yl) -tetrathiopentalen, that was prepared in Example X, with two equivalents of sodium ethylate in ethanol and refluxing for two hours

i becomes a dark solution of lithium-dithiomethoxy-tetrathio-

Ifulvalene dithioanions are obtained. This solution becomes a YO 976 026

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Equivalent nickel acetylacetonate and the solution refluxed overnight. The resulting black precipitate of bis- (dithiomethoxy-tetrathiofulvalen) -bis-dithiolene-nickel

is collected by filtration and washed thoroughly with water, ethanol and acetone. This material is made from
Chlorobenzene recrystallized. Elemental analysis for nickel: 7/5%. Conductivity, measured on a pressed sample: 1 (ohm-cm).

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Claims (4)

PATENT CLAIMS 1. Poly (metal) tetrathiofulvalene tetrathiolate the general formula in which the metal is selected from the group of Ni, Cu, Fe, Cr, Zn, Pt or Ni and Cu. 2. Poly (metal) dithiomethoxy tetrathiofulvalene the general formula ο c ο of r * ι ι \ / / ^S ^ r ^ ^SCH 3 in which the metal is selected from the group of Ni, Cu, Fe, Cr, Zn, Pt or Ni and Cu. 3. Poly (metal) ethylene tetrathiolate of the general formula I χ. y iT ν. ./ in which the metal is selected from the group of Ni, Cu, Fe, Cr, Zn, Pt or Ni and Cu. 4. poly (metal) tetroselenofulvalen-tetraselenate, Poly (metal) -diseleno-methoxy-tetraselenofulvalene and poly (metal) -ethylene-tetraselenate according to the Formulas of claims 1 to 3, in which S is replaced by Se. YO 976 026 8098 40/103? OR ₁ G _1n AL ₁ NSPECTED